Water-insoluble azo-dyestuff



Patented Feb.,26, 1935 UNITED STATES V 1,992,917 WATER-INSOLUBLE'AZO-DYESTUFF Werner Kirst and Max Kerth, Frankfort-on-the- Main,Germany, assignors to General Aniline Works, Inc., NewYork, N. Y.,,acorporation of Delaware No Drawing. Application July 8, 1931, Serial No.549,560. In Germany May 14, 1928 6 Claims.

Our present invention relates to water-insoluble azo-dyestuffs and tofiber dyed therewith.

More particularly itrelates to green water-insoluble azo-dyestuffs whichare obtainableby como bining a monodiazonium saltof an anthraquinonecompound which as non-diazotized amino-com 7 pound has a blue color and,on diazotization, does not undergo any alteration in its structure;apart from the conversion of the amino group intothe diazonium group,with'an acetoacetic acid arylide, an arylamide of a carboxyphenylmethyl-pyrazclone, or with a ureaobtained from a pyrazolone.

We have found that green azo-dyestuffsjare obtainable by combining theabove mono-diazonium compounds obtained from bases which as such have ablue color with the said coupling components, which latter maybedesignated as yellow components. The dyestufis represent a new class ofazo-dyestufis'theymay be produced in substance, on the fiber and on anysubstrata which are adapted for the production of lakes. The shades ofthe dyestuffs vary from yellowishgreen to olive-green according to thecomponents used. The present invention is of great importance,especially as regar-ds the productionof the dyestufis on the fiber,since it has not been possible, hitherto, to produce green dyeings onthe fiber according to the so-called ice-color-method by combining onthe fiber a diazonium compound with a coupling component of thegroupdesig nated above as yellow components. The dyeings and printingshitherto produced by means of such coupling components and diazoniumortetrazonium compounds posses yellow, orange and maroon shades; hence thename yellow components.

By the expression which, on diazotization, do not undergo any alterationin their structure we understand that no amino compounds are to be usedwhich, on diazotization, by the" action of nitrous acid undergo a changein a group or a substituent other than the amino group to be diazotized.By such secondary reaction certain substituents in the compounds may beso altered that, when coupling with the above mentioned yellowcomponents, green tints can no longer be obtained. As an example of anamino compound which on diazotization, besides the conversion of theamino group into the diazonium group, undergoes a further change, theremay be mentioned destroyed;

the 1-amino 4-diethylaminoanthraquinone. This amino compound as such hasa blue color, but it is not suitable for the production of greendyestuffsby coupling its diazo compound with one of,

the above mentioned yellow components since, on

diazotization, the diethylamino-group probablyis The diazonium compoundsproduced from blue colored bases arenot in all cases blue; they may havea color different from that of the amino com- 0- pound. Y

" The present invention is illustrated by a number of examples: it'ispointed outhowever, that the combinations mentioned'in these examplesand-the several components used for their preparation only serve asillustrations and that the invention is not limited to the examplescontained in thisaspecification, Any otheraminocompound which containsan anthraquinone nucleus, has a, blue color and, on diazotization, apartfrom the conversion of the amino group into the diazonium group,undergoes .no altera, tion in its structure, may be used for the purposeof the presentinvention. As regards the components designated yellowcomponents and used v for coupling with the mono-diazonium compounds,the invention, likewise, is not restricted to the particularcomponentsmentioned in the following examples. Various substituted orunsubstituted acetoacetic acid arylides, condensation products fromcarboxyphenyl methyl pyrazolones and aromatic' amines,.or ureas frompyrazolones may be used. Since an object of the present invention is toprovide green water-insoluble azo-dyestuffs of good fastness propertiesand since the dyestuffs produced on the fiber must be fastbto the actionof alkalies; it is to be understood that the presence of substituentswhich would renderv the dyestuffs soluble in water or alkalies and tendto de 4.

preciate the fastness of the dyestuffs to alkalies must be avoided.Substituents of this kind are, for instance, the sulfonic acid and thecarboxylic acid group. Such groups are not included within the scope ofthe appended claims. 1

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto. r

The production of the new dyestuffs on the fiber may be carried outaccording to various methods 5 used in dyeing or printing, for instance,as follows:

(a) Examples 1 to 8:-Method for dyeing cotton or viscose yarn in thetube 50 grams of boiled cotton yarn are treated for half an hour withthe grounding liquor, prepared according to the following examples,squeezed or hydroextracted in order to remove the excess of the liquidand, thereupon, dyed while still wet for half-an-hour in the developingbath. The dyeing obtained is rinsed, treated in a boiling soap bath,rinsed again and dried.

(b) Eaamples 9 to 11:Method for dyeing piece goods The material ispadded with the grounding JaH'! liquor by means of a foulard-machine,squeezed and dried, passe-d through the developing bath and, after ashort airing, washed and soaped in a boiling bath. Examples 12 and13:Method for printing I V cotton or artificial silk materials Thebleached material is padded with the grounding liquor, dried andprinted. with the printing paste. The printed material is dried, rinsedand soaped in a boiling bath containing 3 gramsof soap and 1' gram ofcalcined sodium carbonate per liter, again rinsed and'dried.

(1) I. Grounding liquor 1.75 grams of diacetoacetylrtho-tolidide aredissolved,

while boiling, with i 3.5 cc. of Turkey red oil of 50% strength, 2.6 cc.of caustic soda solution of 34 Be. and i 14 grams of sodium sulfate.This solution is made, up

, with water to 1 liter V II. Developing bath 3.14 grams of 1 amino-4-hexahydrophenylaminoanthraquinone are diazotized with 3.8 cc. ofhydrochloric acid and gram of sodium nitrite; thereupon about 4 grams ofsodium acetate and 25 grams of sodium chloride are added. The Whole is H7 made up with cold water to 1 liter A green dyeing of good fastnessproperties isobtained. The dyestulf formed has the following structure:

(2) I. Grounding liquor 1.75 grams of diacetoacetyl-ortho-tolidide aredissolved as described in Example 1, the solution is made up with waterto 1 liter II. Developing bath grams of l amino 4n-propylaminoanthraquinone are diazotized with cc. of hydrochloric acidand gram of sodium nitrite. Thereupon about grams of sodium acetate andgrams of sodium chloride are added. The solution is made up with coldwater to s-w comes 1 liter v A green dyeing of good iastness propertiesis obtained. The dyestuff formed is represented by the formula i oo 0 HO OH: I V I (3) By using in Example 2 instead of 2.8-grams ofl-amino-4-n-propylaminoanthraquinone, 2.9 grams of1-amino-e-n-butylaminoanthraquinone, a green dyeing of'good fastnessproperties is likewise obtained.

(4) By using inExample 2 instead of 2.8-grams of1-amino-4-n-propylaminoanthraquinone, 2.5 grams of1-amino-4-me'thylaminoanthraquinone, a yellowish-green dyeing of goodfastness properties is obtained.

() I. Grounding liquor 5 grams of2-(4-acetoacetylamino-)phenyl-benzimidazole are dissolved, whileboiling, with 5 v cc. of Turkey red oil, 7.o cc. of caustic sodasolution of 34 B6. and 28 grams of sodium sulfate; the solution is madeup with water to v 1 liter 7 II. Developing bath 3.1 grams ofl-amino-4-phenylaminoauthraquinone are diazotized with 3.8 cc. ofhydrochloric acid and 0.8 gram of sodium nitrite; thereupon about 4grams of sodium acetate and 25 grams of sodium chloride are added, andthe whole is made up with cold water to 1 liter An olive-green dyeing ofgood fastness properites is obtained.

i The dyeetufl-corresponds' to the formula: l a

(6) By using in Example instead of 3.1 grams of l-amino-4phenylaminoanthraquinone, 3.8

grams of 1-amino-4, 4'-N-methylacetylaminophenylaminoanthraquinone, anolive-green dyeing of good fastness properties is'obtained. The

' dyestufi formed has the formula; v

l I O ie-w.

(7) J." Groundinguquar 4.75 grams of";diacetoacetyl-ortho-tolidide arevdissolved as indicated: in Example 1; the solution is madenp'withwater-to I 1 liter I H. Developing bath 3.1 grams of1-amino--phenylaminoanthraquinone are diazotized as indicated in Example5. 'After addition of sodium acetate and sodium chloride, the wholeismade up with cold water to 1 liter. An olive green dyeing of goodfastness properties is obtained. I

The dyestuff .may be represented. by the for mule: :& A it (8) I.Grounding liquor V 1.75 grams of diaeetonacetyl-ortho-tolidide aredissolved as indicated in Example 1 and made up with water to 1 1 1liter II. Developing bath grams of l-methylamlnd(4 aminopheny1)-amino- Vanthraquinone are diuzotized with cc. of hydrochloric acid of 20 B. andgram of sodium nitrite (dissolved). Thereupon the whole is neutralizedby means of about 1-5 grams of Sodium acetate. Thereafter '2 cc.loflacetic acid (of 50% strength) and- 25 grams of sodium chloride areadded. The whole is made up with water to liter A green dyeing of goodfastness properties is obtained; "The dyestuff has the followingstructure:

(13H: ('30 OH Rec-1 TH (9) I. Grounding liquor grams ofdilicetoacetyl-ortho-tolidide are dissolved w1 4 15 grams of sodiumTurkey red oil of 50% strength or sulforicinate (1:1) and 22.5 grams ofcaustic soda solution of 34 B.; the solution is made up with water to 1liter 7 II. Developing bath 6.7 grams of 1,4,5,8-tetraaminoanthraquinoneare diazotized with cc. of formic acid of 96% strength, 50 cc. of icewater, I 28 cc. of hydrochloric acid of 22 Be. and 28 cc. of sodiumnitrite solution (of 30% strength.) Thereupou the'whole is made up withcold water to 1 liter and neutralized, before use, by means of 20 gramsof sodium acetate. 1

The dyed material is exposed to the air for some time and washed andsoaped in a boiling soap bath, containing sodium carbonate.

There may be added to the diazo solution 30 cc. of a copper-chloridesolution of 40 B. and 1 gram of chromic acid per liter, or the dyeingobtained may be after-treated with a copper- II. Developing bath inExamplee; The dyestuff-formedcorrespouds to the formula:

(11) I. Grounding liquor grams of the urea prepared from 1 (para-amino-II. Developing bath.

The developing bath is the same as that used in Example 9. The dyestuffhas the following CH: CH:

I O O. IfiI-HO-OC-HN-O-O-NH-OO-AH-E NH O N 4130 ona NH; A NH:

. (10) I. Grounding liquor grams of the pyrazolone prepared frommeta-aminobenzoic acid-5-chloro-2-toluidide are dissolved with 25 gramsof sodium Turkey red oil of 50% strength an 37.5 cc. of caustic sodasolution of 34 Be. The whole is made up with water to structure:

1 liter in; T HIE-O0 N NE, 1%

NH; NH:

NH: 7 NH;

The following examnles indicate how the dye- V The developing bath isthe same as that used stufis may be Produced on the fiber by Printing!wee-.9

up Ground n liquor 25 grams of diacetoacetyl-ortho-tolidide, I

f 50% strength 25 grams of sodium Turkey red oil 0 or sulforicinate(1:1) an 31.5 cc. o caustic soda solution of 34 Be. are madeintoia'puste and dissolved with 500 cc. ofhot water. The whole is madeup with cold water to 1 liter.

The bleached cotton material is padded with this solution and, afterbeing dried at a temperature of 50 C. to 60 C., printed with thefollowing paste:

II. Printing paste 9 grams of F1,5,3-tetraamino-anthraquinone are dissov in 30 cc. of fgfimic acid of 96% strength and diluted W1 50 cc. of icewater. Thereupon 35 cc. of hydrochloric acid of 22 B. and 35 cc. ofsodium nitriate (of 30% strength) are added, and the whole is diazotizedat a term perature of about 15 C. Thereupon the whole is made up with321 cc. of cold water to 480 grams; this solution is stirred into 500grams of tragacanth (60:1000). Before use,

grams of sodium acetate are added.

1 kilogram The printed material is dried, rinsed and soaped in a boilingsoap bath containing 1 gram of calcined sodium carbonate per liter,again rinsed and dried.

The dyestufi formed is identical with that ohtainable according toExample 9.

(13) Bleached cotton material is padded as described above with thefollowing solution:

'OH: to

Grounding liquor of diacetoacetyhpala-plienxlendiaInide are dissolvedwith grams of sodium Turkey red oil of 50%strength or sulforicinate(1.:1).

grams 37.5 cc'.' of caustic soda solution of 34 Be. and a small quantityof water. The solution is a 7 made up with water to 1 liter The furthertreatment and printing is carried out as stated in Example 12.

We claim: V 1. The azo-dyestufis of the general formula:

0 0 N-HJ-OO-HN NH-OO-dH-N i @Q i 0 Hi0 OH] EN t wherein the His standfor alkyl groups, radicles of the benzene series or hexahydrophenylradicles, which dyestuffs, being free from any substituents renderingthe products soluble in water or alkalies, are insoluble in water andyield, when produced on the fiber, green dyeings.

2. The azo-dyestutf of the formula:

being insoluble in water and yielding, when produced on the fiber, greendyeings of good fastness properties.

3. The azo-dyestuff of the formula:

o E-HJJ-OO-HNWNu-QO-dE-E 0 E0 OH; 7

being insoluble in water and yielding, when pro- 5. Fiber dyed with a.dyestuff referred to in duced on the fiber, green dyeings of good.fastness claim 2. V properties. 6. Fiber dyed with a. dyestuff referredto in 4. Fiber'dyed with a'dyestufl referred to in claim 3. WERNERKIRS'I'.

- r MAX IiERTH.

5 Claim 1.

